Aqueous epoxy resin compsition yielding anti-static soil resistant finish on textiles



United States a Patent Oil ice 4 3,175,987 Patented Mar. 30, 1965 AQUEOUS EPOXY RESIN COMPGSETION YIELD- ING ANTI-STATIC SOIL RESHSTANT FENISH N TEXTILES John Edward Pretka, Sharpley, Wilmington, Del assignor to E. I. du Pont de Nemours and Company, Wilmington, Del., a corporation of Delaware No Drawing. Filed June 30, 1961, Ser. No. 120,906 r 6 Claims. (Cl. 260-292) This invention relates to a novel and useful textile treating composition and textile material processed therewith. More particularly, the invention relates to compositions which provide an-tisoiling and antistatic properties when applied to textile tabrics. It is an object of the present invention to provide a textile finishing composition of matter which will impart antisoiling .and antistatic protection to fabrics which contain synthetic, hydrophobic fibers. Another object is to provide a synthetic, hydrophobic textile bearing an antisoiling and antistatic coating. Other objects will be apparent from the following description of the invention.

In accordance with the present invention a composition of matter is provided comprising an aqueous dispersion containing from about 1% to about total solids of which from about 30% to about 65% is a member of the class consisting of sodium polyacrylate, maleic anhydride, phthalic anhydride and pyromellitic anhydride, the remainder of the said solids being a mixture of polyepox-ide and polyamine of the formula wherein -R- is a divalentradical, -X is a member of the class consisting of amino nitrogen and divalent radical terminating inamino nitrogen, m and n are small whole numbers from about 3 to about 40 and p is an integer no greater than about 10. Since the nature of -R-- is not critical provided it is inert to reaction with amines, it may be any member of the class consisting of while it may contain aza linkages is otherwise hydrocarbon, q being a number from about 6 to about 40. The preparation of these polyamines is discussed in detail in Belgian p-atents'55'4,506, granted January 25, 11957, and 560,446, granted September 14, 1957. In general, the polyethylene glycol dih-alide (e.g. chloride, bromide or iodide) analogue is condensed (with release of hydrogen halide) with an amine, the nitrogen of which contains at least two active hydrogen. Typical of such amines are methylamine, ethylamine, propylamine, butylamine,

amylamine, hexylamine, dodecylamine, .allylamine, monoethanolamine, 3isopropyl-n-propylamine, 3-methoxy-npropylamine, diethylenetriamine, .bis(3-aminopropyl)- i like.

amine, bis(2-aminopropyl) amine, hexamethylene diamine, triethylene tetram-ine, tetnaethylene 'pentamine .and the Such materials are available on the open market, typical products corresponding in general to Example 10 of Belgian patent 560,446 and Example 1 of Belgian patent 554,506.

After the dispersion described above is applied to a textile containing synthetic fibers the polyami-ne defined above is reacted with the polyepoxide to form an antistatic, antisoiling finish. Suitable polyepoxides can be prepared by condensing e-pichlorohydrin with a polyol. A typical example is the condensation product (with elimination of HCl) of glycerine and epichlorohydrin. Preparation of these products is described in detail in British patent 780,288, dated July 31, 1957. Such a material with a molecular weight of between about 280 to 360 is available on the open market under the trademark Eponite 100. Other similar commercial products from the same source include the Epon resins which are diepoxide condensation products ofepichlorohydrin and dimethyl, d-i-para hydroxyphenyl methane and the polyallyl glycidyl ethers). A typical siloxane is 1,3-bis- [-3(2,3 epoxy propoxy)p-ropyl] tetrame-thyldisiloxane sold under the trademark Syl-Kem 90. Reaction of the poly-amine (l) or (II) with the polyepoxide may be conveniently accomplished by heating the shaped structure to which an acidic mixture of the amine and polyepoxide has been applied. y

. In the examples which follow, the treated fabrics are scoured in a bath containing 0.5% by weight-base on the solution of the sodium salt of an unsaturated long chain alcohol sulfate and 0.5 by weight based on the solution of trisodium hexametaphosphate. The dry cleaning operation involves a 25-minute tumble at room temperature using a solution of the following:

48 parts of perchloroethylene (solvent) 2.0 parts dry-cleaning soap (a mahogany oil). 0.2 parts water After tumbling, the fabric is centrifuged for 6 minutes, tumbled for an additional 5 minutes with an equal amount of fresh solvent, then centrifuged again for 5 minutes, dried for 2 minutes, at from 70 C. and steam-pressed. The soiling procedure consists in fastening a 2-inch diameter circle from the treated rug to the cover of a 3 /2 x 8-inch steel cylinder. Lambert soil and %-inch steel balls are placed into the cylinder, and the mixture tumbled in a Launder-Ometer for 12 minutes. The reflectance of the soiled samples is measured using a Model 610 Photovolt Reflectometer with a green tristimulus filter. V

The effectiveness of the static treatment on rugs is measured by the Galvonometer Runway Test. Rug samples, at 20% relative humidity and F., measuring 2 x 10 feet are used. Initially, the subject, wearing shoes with clean and dry leather soles and rubber heels, discharges himself completely to ground. Then he walks a definite number (eighteen) of normal steps on the carpet, and then grasps a probe that connects him through a galvanometer toground. The galvanometer deflection gives a relative comparison of static electricity. With. a galvanometer of 25 ohms resistance shunted with a 60 ohm resistor, static becomes barely evident at 25 deflection units. At 18 deflection units, static tendency is comparable to a cotton rug. At48 deflection units, static becomes moderate and comparable to. that of a clean wool rug. Above 48 deflection units, static becomes increasingly severe. Static tendency offabric swatches is conveniently determined by measurement of surface resistance. These measurements are made under controlled conditions of 25% relative humidity and a temperature of 70 F. 'Current flowing across the fabric is measured accurately with a Beckman, Model V Micromicroammeter, and the surface resistance is then calculated from this and the known applied voltage. For convenience, these values are reported as logarithms of surface resistance. In general, the lower the surface resistance, the lower is the tendency of the fabric to develop a static charge. To indicate more fully the nature of the present invention, the following examples of typical procedures are set forth, it being understood that these ex amples are presented by way of illustration only, and not as limiting the scope of the invention.

EXAMPLE 1' 208 parts of the polyethylene glycol polyamine formed by the condensation of methyl amine and polyethylene glycol 600 dichloride as a 20% solids solution in water is stirred into 1540 parts of Water. 24.6 parts of the polyepoxide prepared from glycerin and epichlorohydrin as described in detail in British Patent 780,288, dated July 21, 1957 and identified therein as Polyether A with an epoxy equivalency of 2.13, and having a molecular weight of 324 and 240 parts of a 25% aqueous solution of polyacrylic acid are then added and the mixture dispersed using a Waring Blendor. The pH is adjusted to 6.1 with aqueous solution of sodium hydroxide.

A 7.5 x 40" piece of 24 oz./yd. 66 nylon (i.e.

polyhexamethylene adipamide) rug is dipped into the mixture described above, squeezed between the rollers of a hand wringer and dried at 212 F. for 30 to 45 minutes in a forced airoven. Curing of the amine epoxide resin occurs during the drying stage. The dried rug is observed to have gained 7.4% by weight of antistatic antisoiling finish based on the original weight of the rug. After the rug is scoured for minutes at 120 F. and dried at 212 F., rubber latex is applied to the backing to give 16 oz./yd. solids. The structure is then dried and cured by heating for 30' minutes at 212 F.

Similarly mixtures are prepared using polybasic organic anhydrides. 208 parts of the same polyethylene glycol polyamine is stirred into 1780 parts of water. 24.6 parts of the same polyepoxide is mixed in and the pH of the solution is then adjusted to 5.5 with 10% acetic acid. 30 parts of anhydride are added and the mixture dispersed using a Waring Blendor. Phthalic anhydride, maleic anhydride and pyromellitic dianhydride are used in the preparation of the mixtures. The mixtures containing the anhydrides are then used to treat 66 nylon rugs as described above and the dried rug samples are observed to have gained 6.07.0% by weight.

Eachofthe rug samples is soiled and the reflectance measured. From the reflectance properties of the described compositions summarized in Table I it is seen that'the treated rugs resist soiling in a more satisfactory manner than does an untreated rug.

Table I Treatment: Reflectance Sodium polyacrylate 40.7 Phthalic anhydride 36.2 Maleic anhydride 37.9 Pyromellitic dianhydride 36.9 Untreated latexed control 32.8

EXAMPLE 2 15 parts of the polyethylene glycol polyamine solution of Example 1, 1.5 parts of the polyepoxide of Example 1, 18 parts of the polyacrylic acid solution of Example 1 and 65.5 parts of water are placed in a stainless steel container and thoroughly mixed. The pH is adjusted to 7.0 with dilute sodium hydroxide solution. -This mixture is then padded onto a 3' x of 24 oz./yd. 66 nylon rug using a Butterworth padder set for 10 y.p.m. and squeezed between the nip of two rollers set at 25 p.s.i. The rug is dried at 250 F, beck scoured for V minutes at 120 F., rinsed thoroughly, dried at 250 F.

and latexed and cured as in Example 1. The treated rug is then used in the Galvanometer Runway Test and found to register 25 deflection units while an untreated 66 nylon rug showed more than 50 deflection units.

EXAMPLE 3 50.0 parts of the polyethylene glycol polyamine of Example 1, 5.0 parts of the polyepoxide of Example 1 and 635 parts of Water are mixed thoroughly, the pH ad-,

justed to 7.0 with glacial acetic acid and 1 part of a 40% aqueous solution of zinc fiuoroborate added with thorough mixing. 60 parts of a 25% aqueous solution of polyacrylic acid is then added with mixing and 10% aqueous sodium hydroxide added until solution of the solids is complete. The pH is found to be 5.0. Swatches of polyacrylonitrile, PA and polyhexametylene adipamide, N are dipped into the mixture prepared as described above and squeezed between rollers of a padder set at 50 p.s.i. The fabrics are heated at 250 F. for several minutes until thoroughly dry, scoured 30 minutes at F., rinsed thoroughly and steam-pressed. The log R values of the fabrics so treated, PA and N are then measured. The treated fabrics are then subjected to the ry-cleaning procedure and the log R values are again determined. Not only do the treated and cleaned fabrics show retained surface resistance, but also they do not show the discoloration and stiffening of similar samples prepared without the addition of sodium polyacrylate, PA and N The log R values of the treated fabrics and of untreated controls, PA and N are summarized in Table II.

50 parts of the polyethylene glycol polyamine of Example 1, 5 parts of the polyepoxide of Example 1 and 665 parts of water are thoroughly mixed. The pH of 96 parts of a 25% aqueous solution of polyacr'ylic. acid is adjusted to 7.0 with dilute sodium carbonate solutionand the neutralized solution added to the amine-epoxide dispersion and thoroughly mixed. A swatch of tropical plain weave fabric woven from a polyethylene terephthalate yarn is dipped into the mixture and hand squeezed to remove excess agent.

The fabric is heated at 285 F. for 5 minutes to dry the fabric and cure the resin, scoured 30 minutes at F., rinsed and dried. The fabric is observed to have gained 3.5% by weight of antistatic antisoiling agent based on the original weight of the fabric. The treated fabric has a log R of 11.4 before dry clearing. After dry cleaning its log R is 11.7 and it shows little or no discoloration. A similarly prepared fabric containing only the amine-epoxide resin has a log R of 10.4 before dry cleaning and, after dry cleaning, has a log R of 13.2 It is highly discolored.

Generally, the treating mixtures of this invention are prepared by dispersing the, ingredients in water at room temperature with vigorous stirring. Although the concentration may vary, dilute mixtures containing from about 1 to about 10% of ingredients are generally preferred. Any such finishing suspension having a concentration suitable to provide from about a 1 to about a 10% solids pickup based on the dry material is satisfactory. The product can be applied to the fabric by conventional methods such as dipping, padding, spraying, and the like.

After removal of excess liquid, by wringing in the case of a textile, it is usually convenient to dry and cure the structure in one operation.

0n forming the mixture, the proportion of components may vary over a wide range. Preferably, the proportion of polyamine:polyepoxide is maintained within the limits of :1 to 1:4 With the polyanionic polymer or the polybasic organic anhydride making up from about 30% to about 65% of the total weight of the applied solids.

Optimum conditions of drying and curing will depend upon the identity of the reactants and the identity of the textile. Generally, however, a temperature of at least about 240 F. is preferred to accomplish efficient drying of the textile. Usually, temperature adjustment is made to permit drying and curing of fabrics in a 3 to 45 minute interval. A temperature of about 212 F. to 300 F. is recommended for most textile materials.

Many modifications of the above will be obvious to those skilled in the art without a departure from the inventive concept.

What is claimed is:

1. A composition of matter comprising an aqueous dispersion containing from about 1% to about 10% total solids of which from about 30% to about 65 is a member of the class consisting of sodium polyacrylate, maleic anhydride, phthalic anhydride and pyromellitic anhydride, the remainder comprising a mixture in proportions between about 4:1 and 1:10 of a polyepoxide and a polyamine of the formula:

wherein --R- is a divalent radical, X- is a member of the class consisting of amino nitrogen and divalent radical terminating in amino nitrogen, m and n are small whole numbers from about 3 to about and p is an integer no greater than about 10.

2. A synthetic hydrophobic textile bearing the dispersed phase of the composition of claim 1.

3. The structure of claim 2 wherein the polyamine has been polyepoxide cured in the presence of sodium polyacrylate.

4. The structure of claim 2 wherein the polyamine has been polyepoxide cured in the presence of maleic anhydride.

5. The structure of claim 2 wherein the polyamine has been polyepoxide cured in the presence of phthalic anhydride.

6. The structure of claim 2 wherein the polyamine has been polyepoxide cured in the presence of pyromellitic anhydride.

References Cited by the Examiner UNITED STATES PATENTS 2,872,427 2/59 Schroeder 26029.6 2,872,428 2/ 59 Schroeder 26029.2 3,070,552 12/62 Tesoro et al. 2602 FOREIGN PATENTS 554,506 1/57 Belgium. 560,446 9/57 Belgium.

LEON J. BERCOVITZ, Primary Examiner.

D. ARNOLD, Examiner. 

1. A COMPOSITION OF MATTER COMPRISING AN AQUEOUS DISPERSION CONTAINING FROM ABOUT 1% TO ABOUT 10% TOTAL SOLIDS OF WHICH FROM ABOUT 30% TO ABOUT 65% IS A MEMBER OF THE CLASS CONSISTING OF SODIUM POLYACRYLATE MALEIC ANHYDRIDE, PHTHALIC ANHYDRIDE AND PYROMELLITIC ANHYDRIDE, THE REMAINDER COMPRISING A MIXTUE IN PROPORTIONS BETWEEN ABOUT 4:1 AND 1:10 OF A POLYEPOXIDE AND A POLYAMINE OF THE FORMULA: 